采用掠入射X射线衍射(GIXRD)、弹性离子反冲(ERD)、氦热解吸(TDS)、扫描电镜(SEM)对直流磁控溅射法制备的含氦Zr-Co、Zr-Ti-Co薄膜进行分析,分别得到样品物相、氦的深度和浓度分布、氦热解吸图谱以及热解吸前后的表面形貌。氦热解吸实...采用掠入射X射线衍射(GIXRD)、弹性离子反冲(ERD)、氦热解吸(TDS)、扫描电镜(SEM)对直流磁控溅射法制备的含氦Zr-Co、Zr-Ti-Co薄膜进行分析,分别得到样品物相、氦的深度和浓度分布、氦热解吸图谱以及热解吸前后的表面形貌。氦热解吸实验曲线反映出Ti的掺杂有利于抑制ZrCo贮氚合金中氦的迁移、聚集和发展,提升相应捕陷位置中氦的释放温度;氦热解吸后,Zr 0.8 Ti 0.2 Co薄膜样品的晶界密度相比ZrCo薄膜样品更低,降低减少了氦泡迁移的通道,延缓高温下氦泡迁移合并的趋势,表明掺杂Ti可提升ZrCo合金的固氦能力,对高温条件下氦的释放具有抑制作用。展开更多
The vacuum arc melting method was used to prepare ZrCo1-xCrx(x=0,0.025,0.05,0.075,0.1)alloys.Afterward,the crystal structure,hydrogenation kinetics,thermodynamic properties,and disproportionation performance of ZrCo1-...The vacuum arc melting method was used to prepare ZrCo1-xCrx(x=0,0.025,0.05,0.075,0.1)alloys.Afterward,the crystal structure,hydrogenation kinetics,thermodynamic properties,and disproportionation performance of ZrCo1-xCrx(x=0-0.1)alloys were investigated.The x-ray diffraction spectra demonstrated that ZrCo1-xCrx(x=0-0.1)alloys contained ZrCo and ZrCo2 phases,and their corresponding hydrides consisted of ZrCoH3 and ZrH phases.The activation behaviors of Cr-substituted samples were significantly promoted.The activation time of ZrCo was 7715 s while that of ZrCo0.9Cr0.1 was 195 s.The improvement of kinetics can be attributed to the catalytic hydrogenation of ZrCr2.The activation energy for the hydrogenation of ZrCo was 44.88-kJ·mol^-1 H2 and decreased to 40.34-kJ·mol^-1 H2 for ZrCo0.95Cr0.05.The plateau pressure and width of the pressure-composition-temperature curves decreased slightly as Cr content increased.The extent of disproportionation of ZrCo was 83.68%after being insulated at 798 K for 10 h and decreased slightly to 70.52%for ZrCo0.9Cr0.1.The improvement of anti-disproportionation performance can be attributed to increase in the activation energy of disproportionation from 167.46-kJ·mol^-1 H2 for ZrCo to 168.28-kJ·mol^-1 H2 for ZrCo0.95Cr0.05.展开更多
Developing a universal and reliable strategy for the modulation of composition and structure of energy storage materials with stable cycling performance is vital for hydrogen and its isotopes storage advanced system,y...Developing a universal and reliable strategy for the modulation of composition and structure of energy storage materials with stable cycling performance is vital for hydrogen and its isotopes storage advanced system,yet still challenging.Herein,an ultra-stable lattice structure is designed and verified to increase atomic chaos and interference for effectively inhibiting disproportionation reaction and improving cycling stability in ZrCo-based hydrogen isotopes storage alloy.After screening in terms of configuration entropy calculation,we construct Zr_(1-2)Nb_(x)Co_(1-2x)Cu_(x)Ni_(x)(x=0.15,0.2,0.25) alloys with increased atomic chaos,and successfully achieve stable isostructural de-/hydrogenation during 100 cycles,whose cycling capacity retentions are above 99%,much higher than 22.4%of pristine ZrCo alloy.Both theoretical analysis and experimental evidences indicate the high thermo-stability of orthorhombic lattice in Zr_(0.8)Nb_(0.2)Co_(0.6)Cu_(0.2)Ni_(0.2) alloy.Notably,the increased atomic chaos and interference in Zr_(0.8)Nb_(0.2)Co_(0.6)Cu_(0.2)Ni_(0.2) alloy causes regulation in hydrogen local chemical neighborhood,thereby confusing the hydrogen release order,which effectively eliminates lattice distortion and unlocks an ultrastable lattice structure.This study provides a new and comprehensive inspiration for hydrogen atoms transport behaviors and intrinsic reason of stable orthorhombic transformation,which can contribute to paving the way for other energy storage materials modulation.展开更多
文摘采用掠入射X射线衍射(GIXRD)、弹性离子反冲(ERD)、氦热解吸(TDS)、扫描电镜(SEM)对直流磁控溅射法制备的含氦Zr-Co、Zr-Ti-Co薄膜进行分析,分别得到样品物相、氦的深度和浓度分布、氦热解吸图谱以及热解吸前后的表面形貌。氦热解吸实验曲线反映出Ti的掺杂有利于抑制ZrCo贮氚合金中氦的迁移、聚集和发展,提升相应捕陷位置中氦的释放温度;氦热解吸后,Zr 0.8 Ti 0.2 Co薄膜样品的晶界密度相比ZrCo薄膜样品更低,降低减少了氦泡迁移的通道,延缓高温下氦泡迁移合并的趋势,表明掺杂Ti可提升ZrCo合金的固氦能力,对高温条件下氦的释放具有抑制作用。
基金the National Natural Science Foundation of China(Grant Nos.21573200,2017YFE0301505,21601165,21401173,21573200,and 51731002).
文摘The vacuum arc melting method was used to prepare ZrCo1-xCrx(x=0,0.025,0.05,0.075,0.1)alloys.Afterward,the crystal structure,hydrogenation kinetics,thermodynamic properties,and disproportionation performance of ZrCo1-xCrx(x=0-0.1)alloys were investigated.The x-ray diffraction spectra demonstrated that ZrCo1-xCrx(x=0-0.1)alloys contained ZrCo and ZrCo2 phases,and their corresponding hydrides consisted of ZrCoH3 and ZrH phases.The activation behaviors of Cr-substituted samples were significantly promoted.The activation time of ZrCo was 7715 s while that of ZrCo0.9Cr0.1 was 195 s.The improvement of kinetics can be attributed to the catalytic hydrogenation of ZrCr2.The activation energy for the hydrogenation of ZrCo was 44.88-kJ·mol^-1 H2 and decreased to 40.34-kJ·mol^-1 H2 for ZrCo0.95Cr0.05.The plateau pressure and width of the pressure-composition-temperature curves decreased slightly as Cr content increased.The extent of disproportionation of ZrCo was 83.68%after being insulated at 798 K for 10 h and decreased slightly to 70.52%for ZrCo0.9Cr0.1.The improvement of anti-disproportionation performance can be attributed to increase in the activation energy of disproportionation from 167.46-kJ·mol^-1 H2 for ZrCo to 168.28-kJ·mol^-1 H2 for ZrCo0.95Cr0.05.
基金financial supports from the National Natural Science Foundation of China (52071286, U2030208 and 51901213)the National Key Research and Development Program of China (2017YFE0301505)。
文摘Developing a universal and reliable strategy for the modulation of composition and structure of energy storage materials with stable cycling performance is vital for hydrogen and its isotopes storage advanced system,yet still challenging.Herein,an ultra-stable lattice structure is designed and verified to increase atomic chaos and interference for effectively inhibiting disproportionation reaction and improving cycling stability in ZrCo-based hydrogen isotopes storage alloy.After screening in terms of configuration entropy calculation,we construct Zr_(1-2)Nb_(x)Co_(1-2x)Cu_(x)Ni_(x)(x=0.15,0.2,0.25) alloys with increased atomic chaos,and successfully achieve stable isostructural de-/hydrogenation during 100 cycles,whose cycling capacity retentions are above 99%,much higher than 22.4%of pristine ZrCo alloy.Both theoretical analysis and experimental evidences indicate the high thermo-stability of orthorhombic lattice in Zr_(0.8)Nb_(0.2)Co_(0.6)Cu_(0.2)Ni_(0.2) alloy.Notably,the increased atomic chaos and interference in Zr_(0.8)Nb_(0.2)Co_(0.6)Cu_(0.2)Ni_(0.2) alloy causes regulation in hydrogen local chemical neighborhood,thereby confusing the hydrogen release order,which effectively eliminates lattice distortion and unlocks an ultrastable lattice structure.This study provides a new and comprehensive inspiration for hydrogen atoms transport behaviors and intrinsic reason of stable orthorhombic transformation,which can contribute to paving the way for other energy storage materials modulation.
